Clustering Web services can improve the quality and efficiency of service discovery and management within a service repository. Nowadays, Web services frequently interact (e.g., composition relation and tag sharing relation) with each other to form a complex and heterogeneous service relationship network. The rich network relations inherently reflect either positive or negative clustering association between Web services, which can be a strong supplement to service semantics for characterizing functional affinities between Web services. In this paper, we propose to cluster Web services by utilizing both description documents and the structural information from the service relationship network. We first learn the content semantic information from service description documents based on the widely used Doc2vec model, and meanwhile, learn the structural semantic information from the service relationship network based on a network representation learning algorithm. Then, we propose to pretrain the content and structural semantic information to obtain the most relevant and unified features through training a service classification model with partially labeled data. Finally, a spectral clustering algorithm is utilized for Web services clustering based on the above unified features with preserved content and structural semantics. Therefore, the proposed services clustering approach takes advantage of both service content semantic and service network structure semantic based similarity between services. Extensive experiments are conducted on a real-world dataset from ProgrammableWeb, composed of 12919 Web API services. Experimental results demonstrate that our approach yields an improvement of 4.78% in precision and 5.4% in recall over the state-of-the-art method.